JPS6339025B2 - - Google Patents
Info
- Publication number
- JPS6339025B2 JPS6339025B2 JP57137753A JP13775382A JPS6339025B2 JP S6339025 B2 JPS6339025 B2 JP S6339025B2 JP 57137753 A JP57137753 A JP 57137753A JP 13775382 A JP13775382 A JP 13775382A JP S6339025 B2 JPS6339025 B2 JP S6339025B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- emulsion
- gloss
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000839 emulsion Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 20
- 239000008199 coating composition Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003513 alkali Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- -1 polyoxyethylene Polymers 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は高光沢の常温乾燥型水性塗料組成物に
関する。
従来、光沢を有する水性塗料組成物は、例えば
特開昭53−24328号公報、特公昭55−49638号公報
には、不飽和カルボン酸などの不飽和単量体を構
成単位とする高分子量の共重合体エマルジヨンが
好ましく適用されており、低分子量の共重合体エ
マルジヨンは耐久性などが劣り、且つエマルジヨ
ンの粒子径が小さ過ぎるために塗料の流動性が悪
く、塗装作業性が劣り、外部用光沢塗料には適さ
ないとされていた。
しかし、本発明者らは低分子量の共重合体エマ
ルジヨンでも特定の樹脂組成を選択し、常温架橋
性を維持すれば高光沢で耐久性のある水性塗料組
成物が得られることを発見し、本発明を完成する
に至つた。即ち、本発明の水性塗料組成物は(1)エ
ポキシ基含有単量体及び／又は水酸基含有単量体
１〜15重量、(2)スチレン及び／又はメタクリル酸
エステル20〜70重量部、(3)アクリル酸エステル80
〜25重量部、(4)不飽和カルボン酸0.5〜５重量部、
上記(1)〜(4)の単量体を構成単位とする数平均分子
量２〜10万である共重合体エマルジヨン（以下該
エマルジヨンと略称）100重量部及び造膜助剤１
〜10重量部から成るものである。
本発明の水性塗料組成物の特徴を詳述する。
該エマルジヨンは、(1)低分子量のため親水性溶
剤との相溶性や顔料とのぬれが非常に優れ、高顔
料容積濃度（以下顔料容積濃度をPVCと略称）
例えば、PVC30％でも高光沢、例えばグロス85
以上が得られる、又基材への密着性も優れる。(2)
重合体中に含有するエポキシ基及び／又は水酸基
と不飽和カルボン酸基との内部架橋に基づいた常
温架橋性で、塗装乾燥後の塗膜は３次元の網目構
造となり、耐久性、例えば耐水性、耐アルカリ
性、耐候性などが向上する。
重合度調整剤、例えばメルカプタン類、具体的
にはｔ―ドデシルメルカプタン、ｎ―ドデシルメ
ルカプタン、オクテルメルカプタンなどを全単量
体に対して0.01〜0.5重量％存在させて、乳化重
合すれば低分子量、即ち数平均分子量２万〜10万
の該エマルジヨンが得られる。
また、該エマルジヨンの乳化重合安定性のため
に界面活性剤としてアニオン性界面活性剤及びノ
ニオン性界面活性剤を使用するが、アニオン性界
面活性剤、例えば
The present invention relates to a high-gloss room-temperature-drying aqueous coating composition. Conventionally, glossy aqueous coating compositions have been proposed, for example, in Japanese Patent Application Laid-open No. 53-24328 and Japanese Patent Publication No. 55-49638, using high-molecular-weight paint compositions containing unsaturated monomers such as unsaturated carboxylic acids as constituent units. Copolymer emulsions are preferably used.Low molecular weight copolymer emulsions have poor durability, and the particle size of the emulsion is too small, resulting in poor paint fluidity and poor painting workability. It was considered unsuitable for glossy paints. However, the present inventors discovered that even with a low molecular weight copolymer emulsion, by selecting a specific resin composition and maintaining crosslinkability at room temperature, a high gloss and durable water-based coating composition could be obtained. The invention was completed. That is, the aqueous coating composition of the present invention contains (1) 1 to 15 parts by weight of an epoxy group-containing monomer and/or a hydroxyl group-containing monomer, (2) 20 to 70 parts by weight of styrene and/or methacrylic acid ester, (3 ) Acrylic acid ester 80
~25 parts by weight, (4) 0.5 to 5 parts by weight of unsaturated carboxylic acid,
100 parts by weight of a copolymer emulsion with a number average molecular weight of 20,000 to 100,000 containing the monomers (1) to (4) above as constituent units (hereinafter referred to as the emulsion) and 1 part of a film-forming aid.
~10 parts by weight. The characteristics of the aqueous coating composition of the present invention will be explained in detail. This emulsion has (1) low molecular weight, excellent compatibility with hydrophilic solvents and wetting with pigments, and high pigment volume concentration (hereinafter referred to as PVC)
For example, even 30% PVC has high gloss, such as gloss 85.
The above properties can be obtained, and the adhesion to the base material is also excellent. (2)
Room-temperature crosslinkability is based on internal crosslinking between epoxy groups and/or hydroxyl groups and unsaturated carboxylic acid groups contained in the polymer, and the coating film after drying has a three-dimensional network structure, which improves durability, such as water resistance. , alkali resistance, weather resistance, etc. are improved. If a polymerization degree regulator, such as mercaptans, specifically t-dodecyl mercaptan, n-dodecyl mercaptan, octel mercaptan, etc. is present in an amount of 0.01 to 0.5% by weight based on the total monomers, emulsion polymerization can result in low molecular weight. That is, the emulsion having a number average molecular weight of 20,000 to 100,000 is obtained. In addition, anionic surfactants and nonionic surfactants are used as surfactants for emulsion polymerization stability of the emulsion.
【式】（Ｒ＝ C8〜C24のアルキル基）[Formula] (R = C 8 to C 24 alkyl group)
【式】（Ｒ＝C8〜9
のアルキル基、ｎ＝２〜20）
RO（CH2CH2O）oSO3Na（Ｒ＝C8〜C9のアルキル
基、ｎ：１〜50）を主体としたものが好ましい。
また、ノニオン性界面活性剤としては、ポリオキ
シエチレンアルキルフエニルエーテル、例えば
HLB13〜18の[Formula] (R = C 8 - 9 alkyl group, n = 2 - 20) RO (CH 2 CH 2 O) o SO 3 Na (R = C 8 - C 9 alkyl group, n: 1 - 50) It is preferable that the main component is
In addition, as a nonionic surfactant, polyoxyethylene alkyl phenyl ether, for example
HLB13~18
【式】
（Ｒ＝C9のアルキル基、ｎ＝10〜50）を挙げるこ
とができる。
以下に本発明を詳細に説明する。
(1) エポキシ基含有単量体は、例えばメタクリル
酸グリシジル、アクリル酸グリシジルなど、水
酸基含有単量体は、例えばメタクリル酸２―ヒ
ドロキシエチル、メタクリル酸２―ヒドロキシ
プロピル、メタクリル酸２，３―ジヒドロキシ
プロピルなど、更にエポキシ基含有単量体及
び／又は水酸基含有単量体の使用量は１〜15重
量部であり、１重量部未満では常温架橋性が低
下して耐水性、耐アルカリ性、耐候性が劣り、
15重量を越えると常温架橋性が不足して耐水
性、耐アルカリ性、耐候性が低下する。
(2) メタクリル酸エステルは、例えばメタクリル
酸メチル、メタクリル酸エチル、メタクリル酸
ブチルなど、更にスチレン及び／又はメタクリ
ル酸エステルの使用量は20〜75重量部であり、
20重量部未満では耐水性、耐アルカリ性及び光
沢が低下し、75重量部を越えると常温造膜性が
劣り、耐水性、耐アルカリ性が低下する。
(3) アクリル酸エステルは、例えばアクリル酸メ
チル、アクリル酸エチル、アクリル酸ブチル、
アクリル酸２―エチルヘキシルなど。アクリル
酸エステルの使用量は80〜25重量部であり80重
量部を越えると耐水性、耐アルカリ性及び光沢
が低下し、25重量部未満では耐水性、耐アルカ
リ性が低下する。
(4) 不飽和カルボン酸は、例えばアクリル酸、メ
タクリル酸、クロトン酸、イタコン酸、マレイ
ン酸、フマル酸など、不飽和カルボン酸の使用
量は0.5〜５重量部であり、0.5重量部未満では
常温架橋性が低下し、且つ重合安定性良好な共
重合体エマルジヨンが得られにくい。また、５
重量部を越えると耐水性、耐アルカリ性が低下
する。
本発明の該エマルジヨンは、前記(1)(2)(3)(4)の単
量体を構成単位とする混合単量体を通常の乳化重
合方法により得られる。即ち、前述の重合度調整
剤を単量体に対し0.01〜0.5重量％、界面活性剤
を単量体に対して通常３〜10重量％使用し、触
媒、具体的には過硫酸塩存在下に通常重合温度約
40〜100℃で１〜８時間混合単量体の乳化重合反
応を実施して数平均分子量２〜10万の共重合体エ
マルジヨンを得る。
該エマルジヨンの数平均分子量が２万未満では
塗膜の耐水性、耐アルカリ性が劣り、10万を越え
ると親水性溶剤との相溶性が劣り、且つ顔料との
濡れが悪くなつて光沢が低下するので好ましくな
い。
該エマルジヨン100重量部に造膜助剤１〜10重
量部を配合する。
造膜助剤は、例えば２，２，４―トリメチル―
１，３―ペンタンジオールモノイソブチレート、
エチレングリコールモノブチルエーテル、エチレ
ングリコールモノブチルエーテルアセテート、ジ
エチレングリコールモノブチルエーテル、ジエチ
レングリコールモノブチルエーテルアセテートな
どの親水性溶剤を挙げることができる。造膜助剤
の使用量が１重量部未満では該エマルジヨンの造
膜性が困難となり、10重量部を越えると該エマル
ジヨンの粘度安定性及び乾燥性が低下するので好
ましくない。
また、本発明の水性塗料組成物に着色顔料、例
えば二酸化チタン、鉛白、酸化亜鉛、炭酸カルシ
ウム、シリカ、酸化鉄、クロムイエロー、クロム
グリーンなど増粘剤、例えばポリエチレンオキサ
イド系高分子化合物、ビニルプロピオネート・ビ
ニルピロリドン共重合体など消泡剤、防腐剤、分
散剤などを必要に応じて添加してもよい。
以下に本発明の実施例及び比較例を示す。なお
部又は％は重量基準を示す。
実施例 １
重合缶に水40部、界面活性剤〔Aerosol Ａ―
501：アルキルアリルスルホン酸ソーダ及びノニ
オンNS―204.5：ポリオキシエチレンアルキルフ
エノールエーテル（ポリオキシエチレンの付加モ
ル数4.5モル）日本油脂社製〕4.8部を入れ、加熱
溶解し、85℃で過硫酸カリウム0.2部を入れ、下
記第１表の単量体混合物及びターシヤリードデシ
ルメルカプタン0.05部を90℃で５時間かけて逐次
添加し、1.5時間保持後、共重合反応を終了し、
アンモニア水８部で中和し、固形分50％、数平均
分子量約８万のエマルジヨンを得た。該エマルジ
ヨン100部に造膜助剤（ジエチレングリコールモ
ノブチルエーテルアセテート）７部を混合して造
膜温度約０℃の水性塗料組成物を得た。
これの耐水性、耐候性及び耐アルカリ性はフレ
キシブルボードにハケで約150g/m2（ウエツト）
塗布し、３日間室温乾燥後、耐候性はそのまゝ
WOM（促進耐候試験機）にかけ、耐水性及び耐
アルカリ性は40℃で１ケ月間水又はアルカリに浸
漬して評価し、光沢はコントラスト紙に６ミルの
アプリケータで塗布し、60゜鏡面反射率を測定し
た結果を第２表に示した。
また、該水性塗料組成物467部に分散剤（エマ
ルジツト：16）９部、二酸化チタン（Ｒ―900）
204部、消泡剤1.0部、増粘剤（ビニルプロピオネ
ート・ビニルピロリドン共重合体）3.0部、水35
部を添加混合したもの、光沢はコントラスト紙に
６ミルのアプリケータで塗布し、60鏡面反射率を
測定した結果、顔料容積濃度（以下PVCと略称）
20で93であつた。
実施例 ２〜５
第１表の単量体混合物を実施例１でターシヤリ
ードデシルメルカプタン0.06部の他は実施例１を
全く同様に乳化重合して固形分50％、数平均分子
量約７万のエマルジヨンを得た。
該エマルジヨン100部に造膜助剤（エチレング
リコールモノブチルエーテルアセテート）を夫々
７，２，２，４各部を混合して造膜温度約０℃の
水性塗料組成物を得た。これの耐水性、耐アルカ
リ性、耐候性及び光沢の評価は実施例１と同様に
行い、その結果を第２表に示した。
また、実施例１と同様に配合した該水性塗料組
成物の着色物の光沢はPVC20で夫々93、95、97、
96であつた。
比較例 １〜３
第１表の単量体混合物を実施例１で重合度調整
剤を使用しない他は実施例１と同様に乳化重合を
行い、固形分50％、数平均分子量約20万のエマル
ジヨンを得た。
該エマルジヨン100部に造膜助剤（ジエチレン
グリコールモノブチルエーテルアセテート）７部
を混合して造膜温度約０℃の水性塗料組成物を得
た。
これらの耐水性、耐アルカリ性、耐候性及び光
沢の評価は実施例１と同様に行い、その結果を第
２表に示した。
また、実施例１と同様に配合した該水性塗料組
成物の着色物の光沢はPVC20で60〜70であつた。[Formula] (R= C9 alkyl group, n=10-50) can be mentioned. The present invention will be explained in detail below. (1) Examples of epoxy group-containing monomers include glycidyl methacrylate and glycidyl acrylate; examples of hydroxyl group-containing monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2,3-dihydroxy methacrylate. The amount of epoxy group-containing monomer and/or hydroxyl group-containing monomer such as propyl used is 1 to 15 parts by weight, and if it is less than 1 part by weight, crosslinking property at room temperature decreases, resulting in poor water resistance, alkali resistance, and weather resistance. is inferior,
If the weight exceeds 15%, crosslinkability at room temperature will be insufficient, resulting in decreased water resistance, alkali resistance, and weather resistance. (2) The methacrylic ester is, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc., and the amount of styrene and/or methacrylic ester used is 20 to 75 parts by weight,
If it is less than 20 parts by weight, water resistance, alkali resistance and gloss will be reduced, and if it exceeds 75 parts by weight, room temperature film forming properties will be poor and water resistance and alkali resistance will be reduced. (3) Acrylic esters include, for example, methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, etc. The amount of acrylic ester used is 80 to 25 parts by weight; if it exceeds 80 parts by weight, the water resistance, alkali resistance and gloss will decrease, and if it is less than 25 parts by weight, the water resistance and alkali resistance will decrease. (4) Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.The amount of unsaturated carboxylic acid used is 0.5 to 5 parts by weight, and less than 0.5 parts by weight. Room-temperature crosslinkability decreases, and it is difficult to obtain a copolymer emulsion with good polymerization stability. Also, 5
If the amount exceeds parts by weight, water resistance and alkali resistance will decrease. The emulsion of the present invention is obtained by a conventional emulsion polymerization method using a mixed monomer having the monomers (1), (2), (3), and (4) as constituent units. That is, the above-mentioned degree of polymerization regulator is used in an amount of 0.01 to 0.5% by weight based on the monomer, and a surfactant is generally used in an amount of 3 to 10% by weight based on the monomer, and in the presence of a catalyst, specifically a persulfate. Usually the polymerization temperature is approx.
The emulsion polymerization reaction of the mixed monomers is carried out at 40 to 100°C for 1 to 8 hours to obtain a copolymer emulsion having a number average molecular weight of 20,000 to 100,000. If the number average molecular weight of the emulsion is less than 20,000, the water resistance and alkali resistance of the coating film will be poor; if it exceeds 100,000, the compatibility with hydrophilic solvents will be poor, and the wettability with pigments will be poor, resulting in a decrease in gloss. So I don't like it. 1 to 10 parts by weight of a membrane-forming agent is blended into 100 parts by weight of the emulsion. The film forming aid is, for example, 2,2,4-trimethyl-
1,3-pentanediol monoisobutyrate,
Examples include hydrophilic solvents such as ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, and diethylene glycol monobutyl ether acetate. If the amount of the film-forming aid used is less than 1 part by weight, it will be difficult to form a film of the emulsion, and if it exceeds 10 parts by weight, the viscosity stability and drying properties of the emulsion will deteriorate, which is not preferred. The aqueous paint composition of the present invention may also contain colored pigments, such as titanium dioxide, white lead, zinc oxide, calcium carbonate, silica, iron oxide, chrome yellow, chrome green, etc. Thickeners, such as polyethylene oxide polymer compounds, vinyl Antifoaming agents such as propionate/vinylpyrrolidone copolymer, preservatives, dispersants, etc. may be added as necessary. Examples and comparative examples of the present invention are shown below. Note that parts and percentages are based on weight. Example 1 40 parts of water and surfactant [Aerosol A-] were added to a polymerization can.
501: Sodium alkylallylsulfonate and nonionic NS-204.5: Add 4.8 parts of polyoxyethylene alkyl phenol ether (number of moles of polyoxyethylene added: 4.5 moles, manufactured by NOF Corporation), heat and dissolve, and add potassium persulfate at 85℃. 0.2 part of the monomer mixture shown in Table 1 below and 0.05 part of tertiary lead decyl mercaptan were added sequentially at 90°C over 5 hours, and after holding for 1.5 hours, the copolymerization reaction was completed.
The mixture was neutralized with 8 parts of aqueous ammonia to obtain an emulsion with a solid content of 50% and a number average molecular weight of about 80,000. 7 parts of a film-forming agent (diethylene glycol monobutyl ether acetate) was mixed with 100 parts of the emulsion to obtain an aqueous coating composition having a film-forming temperature of about 0°C. The water resistance, weather resistance and alkali resistance of this product is approximately 150g/m 2 (wet) when brushed onto a flexible board.
After applying and drying at room temperature for 3 days, the weather resistance remains the same.
Water resistance and alkali resistance were evaluated by immersion in water or alkali for one month at 40℃ using WOM (accelerated weathering tester).Gloss was evaluated by applying to contrast paper with a 6 mil applicator and measuring 60° specular reflectance. The results of the measurements are shown in Table 2. In addition, 467 parts of the aqueous coating composition, 9 parts of a dispersant (emulsion: 16), and titanium dioxide (R-900) were added.
204 parts, antifoaming agent 1.0 parts, thickener (vinyl propionate/vinyl pyrrolidone copolymer) 3.0 parts, water 35 parts
The gloss was applied to contrast paper with a 6 mil applicator, and the specular reflectance was measured to give the pigment volume concentration (hereinafter abbreviated as PVC).
It was 93 at 20. Examples 2 to 5 The monomer mixtures shown in Table 1 were subjected to emulsion polymerization in exactly the same manner as in Example 1 except for 0.06 part of tertiary lead decyl mercaptan to obtain a polymer having a solid content of 50% and a number average molecular weight of about 70,000. I got an emulsion. 7, 2, 2, and 4 parts of a film forming aid (ethylene glycol monobutyl ether acetate) were mixed with 100 parts of the emulsion to obtain an aqueous coating composition having a film forming temperature of about 0°C. The water resistance, alkali resistance, weather resistance and gloss of this product were evaluated in the same manner as in Example 1, and the results are shown in Table 2. Furthermore, the gloss of the colored products of the aqueous paint composition formulated in the same manner as in Example 1 was 93, 95, 97, and 97, respectively, for PVC20.
It was 96. Comparative Examples 1 to 3 The monomer mixtures shown in Table 1 were subjected to emulsion polymerization in the same manner as in Example 1 except that the degree of polymerization regulator was not used. I got an emulsion. 7 parts of a film-forming agent (diethylene glycol monobutyl ether acetate) was mixed with 100 parts of the emulsion to obtain an aqueous coating composition having a film-forming temperature of about 0°C. The evaluation of water resistance, alkali resistance, weather resistance and gloss was carried out in the same manner as in Example 1, and the results are shown in Table 2. Furthermore, the gloss of the colored product of the aqueous coating composition formulated in the same manner as in Example 1 was 60 to 70 on PVC20.
【表】【table】
【表】【table】
Claims (1)
含有単量体 １〜15重量部 (2) スチレン及び／又はメタクリル酸エステル
20〜75重量部 (3) アクリル酸エステル 80〜25重量部 (4) 不飽和カルボン酸 0.5〜５重量部 上記(1)〜(4)の単量体を構成単位とする数平均分
子量２〜10万である共重合体エマルジヨン100重
量部及び造膜助剤１〜10重量部から成る水性塗料
組成物。[Claims] 1 (1) Epoxy group-containing monomer and/or hydroxyl group-containing monomer 1 to 15 parts by weight (2) Styrene and/or methacrylic acid ester
20 to 75 parts by weight (3) Acrylic acid ester 80 to 25 parts by weight (4) Unsaturated carboxylic acid 0.5 to 5 parts by weight Number average molecular weight of monomers (1) to (4) above as constituent units 2 to 2 An aqueous coating composition comprising 100 parts by weight of a copolymer emulsion having a molecular weight of 100,000 and 1 to 10 parts by weight of a film-forming agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13775382A JPS5927969A (en) | 1982-08-06 | 1982-08-06 | Water-base coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13775382A JPS5927969A (en) | 1982-08-06 | 1982-08-06 | Water-base coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5927969A JPS5927969A (en) | 1984-02-14 |
| JPS6339025B2 true JPS6339025B2 (en) | 1988-08-03 |
Family
ID=15206025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13775382A Granted JPS5927969A (en) | 1982-08-06 | 1982-08-06 | Water-base coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5927969A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0290128U (en) * | 1988-12-28 | 1990-07-17 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540740A (en) * | 1983-04-04 | 1985-09-10 | Ppg Industries, Inc. | Cross-linked polymeric microgel prepared from polymerizing epoxy-containing monomer in the presence of an acid |
| CN106905465A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | A kind of manufacture method of resin, the resin and the aqueous ink using the resin |
| JP7409331B2 (en) * | 2021-02-04 | 2024-01-09 | 日信化学工業株式会社 | Coating composition, coating film, and article having the film |
-
1982
- 1982-08-06 JP JP13775382A patent/JPS5927969A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0290128U (en) * | 1988-12-28 | 1990-07-17 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5927969A (en) | 1984-02-14 |
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